CN112851940A - 一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料及其应用 - Google Patents
一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料及其应用 Download PDFInfo
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Abstract
本发明涉及阻燃材料和光电领域,具体地讲,涉及一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料及其应用。在保护气氛下,将黑磷或黑磷烯分散于非质子极性有机溶剂;再加入聚酰亚胺体系的酸酐和聚酰亚胺体系的胺,而后使黑磷或黑磷烯充分剥离成纳米级分散于体系中,控制物料温度为室温或低于室温,反应形成聚酰亚胺酸插层和/或包覆黑磷烯,最终升温至脱除溶剂,固化反应一段时间,制备聚酰亚胺/黑磷烯纳米杂化材料。不仅提升材料的各项力学性能,特别是提高聚酰亚胺的热尺寸稳定性和降低其吸水率,还拓宽了聚酰亚胺在光电领域的应用。
Description
技术领域
本发明涉及阻燃材料和光电领域,更具体地,涉及一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料及其应用。
背景技术
聚酰亚胺(PI)是一种特种工程塑料,广泛应用于航空航天、微电子和光电领域。它具有优良的化学稳定性、耐磨性、耐高温性能、电绝缘性和力学性能。然而,聚酰亚胺的酰亚胺键导致吸水率高,分子主链上的苯环和酰亚胺环导致热尺寸稳定性差等缺点限制了其在高温和精密状态下的应用。无机纳米材料具有很低的热膨胀系数和较低的吸水性,适合改进PI的缺点。传统的无机纳米粒子主要有SiO2、TiO2、POSS、粘土和碳纳米管等。然而,这些无机纳米粒子仍存在与PI相容性差、分散不均、易团聚和沉降等问题。即使利用有机表面改性剂对无机纳米粒子进行有机改性,提高无机纳米粒子与PI基体的相容性,但又存在有机改性剂对PI体系阻聚,有机改性过程繁琐等问题。
黑磷烯作为一种新无机二维纳米材料应用于聚酰亚胺鲜有报道。黑磷烯可由黑磷经机械剥离法和液相剥离法制得。液相剥离法更具其优势,其原理是当化学溶剂的表面能与二维材料相匹配时,溶剂与二维材料之间的相互作用可以平衡剥离该材料所需的能量,通过超声就可把块体材料剥离成片层材料。液相剥离法制备原子层黑磷具有产量较高、设备要求低等优势,同时有机试剂的存在可减缓其降解,但所得产品尺寸小且有机溶剂难以去除。
经检索,鲜有技术涉及黑磷烯原位改性聚酰亚胺的报道。检索到的一篇授权专利:一种黑磷改性的聚酰亚胺复合材料及其制备方法和应用(CN109880365B)。该专利并未涉及黑磷烯,未涉及聚酰亚胺的聚合,该专利只是利用已聚合好的聚酰亚胺粒子和黑磷等物质于无水乙醇中混合,再除去乙醇得到干混料,最后加压烧结,制得黑磷改性聚酰亚胺复合材料。其中的黑磷只是作为一种摩擦的润滑剂,其根本上是一种聚合物与无机粒子的熔融共混。
发明内容
本发明主要针对聚酰亚胺无机纳米杂化材料中,无机粒子分散性差、相容性差和易团聚等缺点。另外,针对黑磷烯易降解且难以大量和聚合物复合的缺点。提供一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料,该复合材料利用含有聚酰亚胺体系的溶剂和单体对黑磷进行插层,再利用超声波剥离法进一步使黑磷在体系中剥离成黑磷烯,利用预聚的聚酰亚胺酸使黑磷烯纳米级分散于聚酰亚胺体系中,最终升温固化一步法制备聚酰亚胺/黑磷烯纳米杂化材料。不仅提升材料的各项力学性能,特别是提高PI的热尺寸稳定性和降低其吸水率,还拓宽了其在光电领域的应用。
本发明通过以下技术方案予以实现:
公开的一步法制备聚酰亚胺/黑磷烯纳米杂化材料,在保护气氛下,将黑磷或黑磷烯分散于非质子极性有机溶剂;再加入聚酰亚胺体系的酸酐和胺,而后使黑磷或黑磷烯充分剥离成纳米级分散于体系中,控制物料温度为室温或低于室温,反应形成聚酰亚胺酸插层和/或包覆黑磷烯,最终升温至脱除溶剂,固化反应一段时间,制备聚酰亚胺/黑磷烯纳米杂化材料。
进一步地,所述黑磷包括块状黑磷和低维黑磷,所述块状黑磷为由白磷或红磷在高温高压下转化而来,所述黑磷烯由液相剥离法在聚酰亚胺体系中制备。
进一步地,按质量组分计:黑磷或黑磷烯1~50份,非质子极性溶剂100~400份,聚酰亚胺体系的酸酐20~100份,聚酰亚胺体系的胺20~200份。
进一步地,所述黑磷烯的粒径为10nm~100μm,片层厚度为1~200nm。
进一步地,所述黑磷的粒径为100μm~100mm,片层厚度为200nm~10mm。
进一步地,所述升温至脱除溶剂的温度为200~400℃,固化1~24h。
进一步地,所述保护气体为氮气、氩气的任意一种或两种混合。
进一步地,所述黑磷或黑磷烯的剥离通过超声波液相剥离法,所述超声波功率为100~7200W,频率为20~100KHZ。超声波液相剥离法使黑磷或黑磷烯进一步剥离成纳米级。
进一步地,所述非质子极性溶剂为无水的乙腈,N-甲基吡咯烷酮,二甲基甲酰胺,二甲基乙酰胺,1,3-二甲基-2-咪唑啉酮,二甲基亚砜,六甲基磷酰三胺,N,N-二甲基丙烯基脲中的至少一种。
进一步地,所述聚酰亚胺体系的酸酐为单元酐类化合物、苯二酐类化合物和联苯二酐类化合物。例如,均苯四甲酸二酐、偏苯三酸酐、二苯酮二酐、联苯二酐、二苯醚二酐、六氟二酐等中的至少一种。
进一步地,所述胺为单元胺、苯二胺、萘二胺、联苯胺类和二氨基二苯甲烷类。例如,对苯二胺、间苯二胺、领苯二胺、2,4-二氨基苯酚、2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、4,4´-二氨基二苯甲烷(MDA)等中的至少一种。
本申请中的非质子极性溶剂、酸酐和胺类三者均可以对黑磷或黑磷烯进行插层。
上述聚酰亚胺/黑磷烯纳米杂化材料可以制备成聚酰亚胺薄膜,聚酰亚胺纤维等各种材料,提高各项性能,特别是应用于光电领域。
本发明一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料创造性地在聚酰亚胺体系中对黑磷进行超声波液相剥离,先通过体系的溶剂和单体对黑磷进行插层,经液相剥离后,利用预聚的聚酰亚胺酸对黑磷烯进行进一步插层和包覆,使其达到纳米级分散而不团聚。再结合超波的强度和持续时间控制黑磷烯的尺寸,通过聚酰亚胺体系的酸酐和聚酰亚胺体系的胺的选择控制黑磷烯的分散程度。该方法通过聚酰亚胺体系的溶剂和单体,使黑磷与氧气、水隔绝,从而阻止黑磷被降解,且使黑磷在体系中一步法剥离成黑磷烯制备聚酰亚胺/黑磷烯纳米杂化材料。
与现有技术相比,本发明具有如下有益效果:
本发明提供的一步法黑磷烯原位改性聚酰亚胺,创造性地利用体系的溶剂和单体保护黑磷烯不被降解,且在体系聚合过程中控制黑磷烯的尺寸。该方法通过超声波液相剥离法和聚酰亚胺聚合体系的结合,一步法制备纳米杂化材料,能促使黑磷烯和聚酰亚胺大量复合,克服了黑磷烯产量小、利用率低的缺点。制备得到的纳米杂化材料,不仅使黑磷烯达到纳米级效应提高各项力学性能,而且能更好地发挥黑磷烯的光电效应。
本申请利用聚酰亚胺的非质子极性有机溶剂和单体对黑磷进行插层,再利用超声波液相剥离法使黑磷进一步剥离成黑磷烯,分散于聚酰亚胺预聚体系中,进一步预聚的聚酰亚胺酸对黑磷烯进行包覆,最后聚酰亚胺酸在高温下脱除体系溶剂固化成聚酰亚胺,一步法制得聚酰亚胺/黑磷烯纳米杂化材料。该方法很好地结合了液相剥离法的优势和聚酰亚胺聚合过程中非质子有机溶剂对黑磷的保护。同时聚酰亚胺的固化也很好解决了液相剥离法制得的黑磷烯表面的有机溶剂难以去除的问题。最终制得的聚酰亚胺/黑磷烯纳米杂化材料能很好的提高聚酰亚胺的热尺寸温度性,并降低其吸水率。
附图说明
图1为实施例1所制备的聚酰亚胺/黑磷烯纳米杂化材料流延成膜的薄膜断面SEM图。
图2为实施例2所制备的聚酰亚胺/黑磷烯纳米杂化材料流延成膜的薄膜断面SEM图。
具体实施方式
下面结合附图和具体实施例进一步详细说明本发明。除非特别说明,本发明实施例使用的各种原料均可以通过常规市购得到,或根据本领域的常规方法制备得到,所用设备为实验常用设备。除非另有定义或说明,本文中所使用的所有专业与科学用语与本领域技术熟练人员所熟悉的意义相同。
本发明的一步法制备聚酰亚胺/黑磷烯纳米杂化材料,在保护气氛下,将黑磷或黑磷烯分散于非质子极性有机溶剂;再加入聚酰亚胺体系的酸酐和胺,而后使黑磷或黑磷烯充分剥离成纳米级分散于体系中,控制物料温度为室温或低于室温,反应形成聚酰亚胺酸插层和/或包覆黑磷烯,最终升温至200~400℃,脱除溶剂,固化反应1~24h,制备聚酰亚胺/黑磷烯纳米杂化材料。
按质量组分计:黑磷或黑磷烯1~50份,非质子极性溶剂100~400份,聚酰亚胺体系的酸酐20~100份,聚酰亚胺体系的胺20~200份。黑磷烯的粒径为10nm~100μm,片层厚度为1~200nm,黑磷的粒径为100μm~100mm,片层厚度为200nm~10mm。
本发明公开的黑磷包括块状黑磷和低维黑磷,所述块状黑磷为由白磷或红磷在高温高压下转化而来,低维黑磷由块状黑磷经机械剥离法或液相剥离法方法制备。
非质子极性溶剂为无水的乙腈,N-甲基吡咯烷酮,二甲基甲酰胺,二甲基乙酰胺,1,3-二甲基-2-咪唑啉酮,二甲基亚砜,六甲基磷酰三胺,N,N-二甲基丙烯基脲中的至少一种。
聚酰亚胺体系的酸酐为单元酐类化合物、苯二酐类化合物和联苯二酐类化合物。例如,均苯四甲酸二酐、偏苯三酸酐、二苯酮二酐、联苯二酐、二苯醚二酐、六氟二酐等中的至少一种。
聚酰亚胺体系的胺为单元胺、苯二胺、萘二胺、联苯胺类和二氨基二苯甲烷类。例如,对苯二胺、间苯二胺、领苯二胺、2,4-二氨基苯酚、2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、4,4´-二氨基二苯甲烷(MDA)等中的至少一种。
其具体的实施方案如下。
实施例1
本实施例中的一步法制备聚酰亚胺/黑磷烯纳米杂化材料的制备方法,包括以下步骤:
S1.将400g无水无氧的N-甲基吡咯烷酮(NMP)加入预聚反应器中,粒径为50~100μm、片层厚为100~200nm的1g黑磷,50g均苯四甲酸二酐和25g对苯二胺一起加入预聚反应器中,与NMP混合,整个反应系统通有循环氮气或氩气气体,排除体系内空气和少量水分;
S2.对预聚反应器进行超声波处理,超声波功率为100W,频率为100KHZ。超声波液相法使体系中的黑磷剥离成黑磷烯,超声波处理12h,利用内外盘管通冷却水对体系进行冷却,保持反应温度为室温,制备聚酰亚胺酸包覆黑磷烯预聚体混合液;
S3.在循环氮气或氩气保护下,体系带走溶剂NMP回收利用,260℃流延固化2h,制得聚酰亚胺/黑磷烯纳米杂化材料薄膜。
本方法制得的聚酰亚胺/黑磷烯纳米杂化材料薄膜通过扫描电子显微镜对其薄膜断面进行微观组织观察。由图1知。黑磷烯呈较为规整的方形片层嵌于聚酰亚胺基体中。
实施例2
本实施例中的一步法制备聚酰亚胺/黑磷烯纳米杂化材料的制备方法,包括以下步骤:
S1. 将100g无水无氧的二甲基乙酰胺(DMAC)加入聚反应器中,粒径为20~50μm、片层厚为200~500nm的1g黑磷,与DMAC混合,整个反应系统通有循环氮气气体,排除体系内空气和少量水分,再超声波液相法处理体系12h,超声波功率为6000W,频率为30~40KHZ。
S2. 利用循环水和循环氮气冷却体系至室温,再加入20g偏苯三酸酐和17g萘二胺一起加入预聚反应器中,反应12h,制备聚酰亚胺酸包覆黑磷烯预聚体混合液。
S3. 在循环氮气保护下,体系带走溶剂DMAC回收利用,200℃流延固化12h,制得聚酰亚胺/黑磷烯纳米杂化材料薄膜。
本方法制得的聚酰亚胺/黑磷烯纳米杂化材料薄膜的断面通过扫描电子显微镜对其进行微观组织观察。由图2知。黑磷烯与实例1相比更为细化,超声液相处理、聚酰胺酸的插层和包覆破坏了黑磷烯的规整性,使其和聚酰亚胺基体结合更紧密。
实施例3
本实施例中的一步法制备聚酰亚胺/黑磷烯纳米杂化材料的制备方法,包括以下步骤:
S1. 将400g无水无氧的二甲基甲酰胺(DMF)加入预聚反应器中,粒径为100~200nm、厚为50~100nm的2g黑磷烯,100g二苯醚二酐和65g4,4´-二氨基二苯甲烷(MDA)一起加入预聚反应器中,与DMF混合,整个反应系统通有循环氮气气体,排除体系内空气和少量水分;
S2. 对预聚反应器进行超声波处理,超声波液相法使体系中的黑磷剥离成黑磷烯,超声波功率2400~2600W,频率28~30KHz,处理24h,利用内外盘管通冷却水对体系进行冷却,保持反应温度为室温,制备聚酰亚胺酸包覆黑磷烯预聚体混合液;
S3.在循环氮气保护下,体系带走溶剂DMF回收利用,280℃流延固化4h,制得聚酰亚胺/黑磷烯纳米杂化材料薄膜。
实施例4
本实施例中的一步法制备聚酰亚胺/黑磷烯纳米杂化材料的制备方法,包括以下步骤:
S1. 将400g无水无氧的二甲基亚砜加入聚反应器中,粒径为100μm厚为100mm的10g黑磷与二甲基亚砜混合,整个反应系统通有循环氮气气体,排除体系内空气和少量水分,再超声波液相法处理体系,其超声波功率为6000~7000W,频率为40~60KHZ,处理24h;
S2. 利用循环水和循环氮气冷却体系至室温,再加入200g偏苯三酸酐和206g二氨基二苯甲烷一起加入预聚反应器中,反应12h,制备聚酰亚胺酸包覆黑磷烯预聚体混合液。
S3. 在循环氮气保护下,体系带走溶剂二甲基亚砜回收利用,300℃流延固化1h,制得聚酰亚胺/黑磷烯纳米杂化材料薄膜。
本发明将黑磷烯改性聚酰亚胺,在聚酰亚胺聚合过程中加入黑磷烯。创造性地利用聚酰亚胺聚合过程中的非质子极性溶剂和单体保护黑磷不受空气影响而分解,并且使黑磷在超声波或机械作用力下剥离成纳米级黑磷烯,再利用聚酰亚胺体系的酸酐和胺反应成的聚酰亚胺酸包覆和分隔纳米级黑磷稀,使其不易团聚,最终固化聚酰亚胺酸制备聚酰亚胺/黑磷烯纳米复合材料。通过对聚酰亚胺单体的选择,再结合黑磷烯大小尺寸的选择,制备各种不同特性的复合材料。该复合材料利用聚酰亚胺聚合过程中所用的溶剂和单体保护黑磷烯,利用聚酰亚胺单体和聚酰亚胺酸阻碍黑磷烯团聚,有利于黑磷烯纳米级分散于材料基体中,不仅能发挥黑磷烯的阻燃性能,而且黑磷烯的纳米级效应能提升材料的各项力学性能和耐热性能,特别是黑磷烯的光电效应可以拓宽聚酰亚胺在光电领域的应用。
Claims (10)
1.一种一步法制备聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,在保护气氛下,将黑磷或黑磷烯分散于非质子极性有机溶剂;再加入聚酰亚胺体系的酸酐和聚酰亚胺体系的胺,而后使黑磷或黑磷烯充分剥离成纳米级分散于体系中,控制物料温度为室温或低于室温,反应形成聚酰亚胺酸插层和/或包覆黑磷烯,最终升温至脱除溶剂,固化反应一段时间,制备聚酰亚胺/黑磷烯纳米杂化材料。
2.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,按质量组分计:黑磷或黑磷烯1~50份,非质子极性溶剂100~400份,聚酰亚胺体系的酸酐20~100份,聚酰亚胺体系的胺20~200份。
3.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述黑磷烯的粒径为10nm~100μm,片层厚度为1~200nm。
4.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述黑磷的粒径为100μm~100mm,片层厚度为200nm~10mm。
5.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述升温至脱除溶剂的温度为200~400℃,固化1~24h。
6.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述黑磷或黑磷烯充分剥离通过超声波液相剥离法,所述超声波功率为100~7200W,频率为20~100KHZ。
7.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述非质子极性溶剂为无水的乙腈,N-甲基吡咯烷酮,二甲基甲酰胺,二甲基乙酰胺,1,3-二甲基-2-咪唑啉酮,二甲基亚砜,六甲基磷酰三胺,N,N-二甲基丙烯基脲中的至少一种。
8.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述聚酰亚胺体系的酸酐为单元酐类化合物、苯二酐类化合物和联苯二酐类化合物。
9.根据权利要求1所述聚酰亚胺/黑磷烯纳米杂化材料,其特征在于,所述聚酰亚胺体系的胺为单元胺、苯二胺、萘二胺、联苯胺类和二氨基二苯甲烷类。
10.权利要求1~9任意一项所述聚酰亚胺/黑磷烯纳米杂化材料的应用,其特征在于,制备成聚酰亚胺薄膜,聚酰亚胺纤维材料用于光电领域。
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